Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02810720 2013-03-28
MARINE ENGINE LUBRICATION
FIELD OF THE INVENTION
This invention relates to a trunk piston marine engine lubricating composition
for a medium-speed four-stroke compression-ignited (diesel) marine engine and
lubrication of such an engine.
BACKGROUND OF THE INVENTION
Marine trunk piston engines generally use Heavy Fuel Oil ('HF0') for
offshore running. Heavy Fuel Oil is the heaviest fraction of petroleum
distillate and
comprises a complex mixture of molecules including up to 15% of asphaltenes,
defined as the fraction of petroleum distillate that is insoluble in an excess
of aliphatic
hydrocarbon (e.g. heptane) but which is soluble in aromatic solvents (e.g.
toluene).
Asphaltenes can enter the engine lubricant as contaminants either via the
cylinder or
the fuel pumps and injectors, and asphaltene precipitation can then occur,
manifested
in 'black paint' or 'black sludge' in the engine. The presence of such
carbonaceous
deposits on a piston surface can act as an insulating layer which can result
in the
formation of cracks that then propagate through the piston. If a crack travels
through
the piston, hot combustion gases can enter the crankcase, possibly resulting
in a
crankcase explosion.
It is therefore highly desirable that trunk piston engine oils ('TPEO's)
prevent
or inhibit asphaltene precipitation. The prior art describes ways of doing
this.
WO 2010/115594 ("594") and WO 2010/115595 ("595") describe the use, in
trunk piston marine engine lubricating oil compositions that contain 50 mass %
or
more of a Group II basestock, of respective minor amounts of a calcium
salicylate
detergent and of a polyalkenyl-substituted carboxylic and anhydride. The data
in
"594" and "595" show that the combination gives rise to improved asphaltene
dispersancy.
CA 02810720 2013-03-28
. .
"594" and "595" are not, however, concerned with the economics of treating
TPEO's to inhibit 'black paint' formation when a Group I base oil is used. A
considerable cost arises from the amount of detergent soap that is used, i.e.
the
detergent other than the basic material. It is now found that, by using
relatively small
additions of the above anhydride, it is possible to achieve good asphaltene
dispersancy properties at lower, and therefore more economic levels, of soap.
SUMMARY OF THE INVENTION
A first aspect of the invention is a trunk piston marine engine lubricating
oil
composition of TBN in the range of 20 to 60, such as 30 to 55, for improving
asphaltene handling in use thereof, in operation of the engine when fuelled by
a heavy
fuel oil, which composition comprises or is made by admixing an oil of
lubricating
viscosity, in a major amount, containing 50 mass % or more of a Group I
basestock,
preferably containing 55 mass % or more of a Group I basestock, and, in
respective
minor amounts:
(A) a calcium alkyl salicylate detergent system providing 40 to 90, such as
50 to 85 or 60 to 80, mmol of calcium alkyl salicylate per kg of the
composition, as determined by titration; and
(B) 1 to 7, such as 1.5 to 5, mass % active ingredient, based on the mass
of
the composition, of a polyalkenyl-substituted carboxylic acid
anhydride, wherein the or at least one polyalkenyl group is derived
from a polyalkene having a number average molecular weight of from
200 to 3,000.
By "system" is meant a single calcium alkyl salicylate detergent or a mixture
of two or more such detergents.
A second aspect of the invention is a method of operating a trunk piston
medium-speed compression-ignited marine engine comprising
(i) fuelling the engine with a heavy fuel oil; and
2
CA 02810720 2013-03-28
(ii) lubricating the crankcase of the engine with a composition
according to
the first aspect of the invention.
A third aspect of the invention is a method of dispersing asphaltenes in a
trunk
piston marine lubricating oil composition during its lubrication of surfaces
of the
combustion chamber of a medium-speed compression-ignited marine engine and
operation of the engine, which method comprises:
(i) providing a composition according to the first aspect of the invention;
(ii) providing the composition in the combustion chamber;
(iii) providing heavy fuel oil in the combustion chamber; and
(iv) combusting the heavy fuel oil in the combustion chamber.
A fourth aspect of the invention is the use of detergent (A) in combination
with component (B) as defined in and in the amounts stated according to the
first
aspect of the invention in a trunk piston marine lubricating oil composition
of TBN in
the range of 20 to 60, such as 30 to 55, for a medium-speed compression-
ignited
marine engine, which composition comprises an oil of lubricating viscosity in
a major
amount and contains 50 mass % or more of a Group I basestock, preferably
contains
55 mass % or more of a Group I basestock, to improve asphaltene handling
during
operation of the engine, fuelled by a heavy fuel oil, and its lubrication by
the
composition.
In this specification, the following words and expressions, if and when used,
have the meanings ascribed below:
"active ingredients" or "(a.i.)" refers to additive material that is not
diluent or
solvent;
3
CA 02810720 2013-03-28
"comprising" or any cognate word specifies the presence of stated features,
steps, or integers or components, but does not preclude the presence or
addition of one or more other features, steps, integers, components or groups
thereof; the expressions "consists of' or "consists essentially of' or
cognates
may be embraced within "comprises" or cognates, wherein "consists
essentially of' permits inclusion of substances not materially affecting the
characteristics of the composition to which it applies;
"major amount" means 50 mass % or more of a composition;
"minor amount" means less than 50 mass % of a composition;
"TBN" means total base number as measured by ASTM D2896.
Furthermore in this specification, if and when used:
"calcium content" is as measured by ASTM 4951;
"phosphorus content" is as measured by ASTM D5185;
"sulphated ash content" is as measured by ASTM D874;
"sulphur content" is as measured by ASTM D2622;
"KV100" means kinematic viscosity at 100 C as measured by ASTM D445.
Also, it will be understood that various components used, essential as well as
optimal and customary, may react under conditions of formulation, storage or
use and
that the invention also provides the product obtainable or obtained as a
result of any
such reaction.
Further, it is understood that any upper and lower quantity, range and ratio
limits set forth herein may be independently combined.
4
CA 02810720 2013-03-28
DETAILED DESCRIPTION OF THE INVENTION
The features of the invention will now be discussed in more detail below.
OIL OF LUBRICATING VISCOSITY
The lubricating oils may range in viscosity from light distillate mineral oils
to
heavy lubricating oils. Generally, the viscosity of the oil ranges from 2 to
40 mm2/sec,
as measured at 100 C.
Natural oils include animal oils and vegetable oils (e.g., castor oil, lard
oil);
liquid petroleum oils and hydrorefined, solvent-treated or acid-treated
mineral oils of
the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of
lubricating
viscosity derived from coal or shale also serve as useful base oils.
Synthetic lubricating oils include hydrocarbon oils and halo-substituted
hydrocarbon oils such as polymerized and interpolymerized olefins (e.g.,
polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated
polybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes));
alkybenzenes (e.g.,
dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2-
ethylhexyl)benzenes);
polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenols); and
alkylated
diphenyl ethers and alkylated diphenyl sulphides and derivative, analogues and
homologues thereof.
Alkylene oxide polymers and interpolymers and derivatives thereof where the
terminal hydroxyl groups have been modified by esterification, etherification,
etc.,
constitute another class of known synthetic lubricating oils. These are
exemplified by
polyoxyalkylene polymers prepared by polymerization of ethylene oxide or
propylene
oxide, and the alkyl and aryl ethers of polyoxyalkylene polymers (e.g., methyl-
polyiso-propylene glycol ether having a molecular weight of 1000 or diphenyl
ether
of poly-ethylene glycol having a molecular weight of 1000 to 1500); and mono-
and
polycarboxylic esters thereof, for example, the acetic acid esters, mixed C3-
C8 fatty
acid esters and C13 oxo acid diester of tetraethylene glycol.
CA 02810720 2013-03-28
Another suitable class of synthetic lubricating oils comprises the esters of
dicarboxylic acids (e.g., phthalic acid, succinic acid, alkyl succinic acids
and alkenyl
succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric
acid,
adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenyl
malonic
acids) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl
alcohol,
2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene
glycol).
Specific examples of such esters includes dibutyl adipate, di(2-ethylhexyl)
sebacate,
di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate,
dioctyl
phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of
linoleic
acid dimer, and the complex ester formed by reacting one mole of sebacic acid
with
two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
Esters useful as synthetic oils also include those made from C5 to C12
monocarboxylic acids and polyols and polyol esters such as neopentyl glycol,
trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
Silicon-based oils such as the polyalkyl-, polyaryl-, polyalkoxy- or
polyaryloxysilicone oils and silicate oils comprise another useful class of
synthetic
lubricants; such oils include tetraethyl silicate, tetraisopropyl silicate,
tetra-(2-
ethylhexyl)silicate, tetra-(4-methyl-2-ethylhexyl)silicate, tetra-(p-tert-
butyl-phenyl)
silicate, hexa-(4-methyl-2-ethylhexyDdisiloxam, poly(methyl)siloxanes and
poly(methylphenyl)siloxanes. Other synthetic lubricating oils include liquid
esters of
phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate,
diethyl
ester of decylphosphonic acid) and polymeric tetrahydrofurans.
Unrefined, refined and re-refined oils can be used in lubricants of the
present
invention. Unrefined oils are those obtained directly from a natural or
synthetic
source without further purification treatment. For example, a shale oil
obtained
directly from retorting operations; petroleum oil obtained directly from
distillation; or
ester oil obtained directly from esterification and used without further
treatment, are
unrefined oils. Refined oils are similar to unrefined oils except that the oil
is further
treated in one or more purification steps to improve one or more properties.
Many
such purification techniques, such as distillation, solvent extraction, acid
or base
extraction, filtration and percolation, are known to those skilled in the art.
Re-refined
6
CA 02810720 2013-03-28
oils are obtained by processes similar to those used to provide refined oils
but begin
with oil that has already been used in service. Such re-refined oils are also
known as
reclaimed or reprocessed oils and are often subjected to additional processing
using
techniques for removing spent additives and oil breakdown products.
The American Petroleum Institute (API) publication "Engine Oil Licensing and
Certification System", Industry Services Department, Fourteenth Edition,
December
1996, Addendum 1, December 1998 categorizes Group 1 base stocks as follows:
Group I base stocks contain less than 90 percent saturates and/or greater than
0.03 percent sulphur and have a viscosity index greater than or equal to 80
and
less than 120 using the test methods specified in Table E-1.
Analytical Methods for Base Stock are tabulated below:
PROPERTY TEST METHOD
Saturates ASTM D 2007
Viscosity Index ASTM D 2270
Sulphur ASTM D 2622
ASTM D 4294
ASTM D 4927
ASTM D 3120
As stated, the oil of lubricating viscosity in this invention contains 50 mass
%
or more of the defined basestock or a mixture thereof. Preferably, it contains
60, such
as 70, 80 or 90, mass % or more of the defined basestock or a mixture thereof
The
oil of lubricating viscosity may be substantially all the defined basestock or
a mixture
thereof.
CALCIUM ALKYL SALICYLATE DETERGENT SYSTEM (A)
A metal detergent is an additive based on so-called metal "soaps", that is
metal
salts of acidic organic compounds, sometimes referred to as surfactants. They
generally comprise a polar head with a long hydrophobic tail. Overbased metal
7
CA 02810720 2013-03-28
detergents, which comprise neutralized metal detergents as the outer layer of
a metal
base (e.g. carbonate) micelle, may be provided by including large amounts of
metal
base by reacting an excess of a metal base, such as an oxide or hydroxide,
with an
acidic gas such as carbon dioxide.
In the present invention, (A) is a calcium alkyl-substituted salicylate
system.
A detergent of such a system typically has the structure shown:
( )il \
1 ¨C Ca"
\ R
2
wherein R is a linear alkyl group. There may be more than one R group attached
to
the benzene ring. The C00" group can be in the ortho, meta or para position
with
respect to the hydroxyl group; the ortho position is preferred. The R group
can be in
the ortho, meta or para position with respect to the hydroxyl group.
Salicylic acids are typically prepared by the carboxylation, by the Kolbe-
Schmitt process, of phenoxides, and in that case, will generally be obtained
(normally
in a diluent) in admixture with uncarboxylated phenol. Salicylic acids may be
non-
sulphurized or sulphurized, and may be chemically modified and/or contain
additional
substituents. Processes for sulphurizing an alkyl salicylic acid are well
known to
those skilled in the art, and are described, for example, in US 2007/0027057.
The alkyl groups advantageously contain 5 to 100, preferably 9 to 30,
especially 14 to 24, carbon atoms.
The term "overbased" is generally used to describe metal detergents in which
the ratio of the number of equivalents of the metal moiety to the number of
equivalents of the acid moiety is greater than one. The term low-based' is
used to
describe metal detergents in which the equivalent ratio of metal moiety to
acid moiety
is greater than 1, and up to about 2.
8
CA 02810720 2013-03-28
By an "overbased calcium salt of surfactants" is meant an overbased detergent
in which the metal cations of the oil-insoluble metal salt are essentially
calcium
cations. Small amounts of other cations may be present in the oil-insoluble
metal salt,
but typically at least 80, more typically at least 90, for example at least
95, mole %, of
the cations in the oil-insoluble metal salt, are calcium ions. Cations other
than
calcium may be derived, for example, from the use in the manufacture of the
overbased detergent of a surfactant salt in which the cation is a metal other
than
calcium. Preferably, the metal salt of the surfactant is also calcium.
Carbonated overbased metal detergents typically comprise amorphous
nanoparticles.
Additionally, there are disclosures of nanoparticulate materials
comprising carbonate in the crystalline calcite and vaterite forms.
The basicity of the detergents may be expressed as a total base number (TBN).
A total base number is the amount of acid needed to neutralize all of the
basicity of
the overbased material. The TBN may be measured using ASTM standard D2896 or
an equivalent procedure. The detergent may have a low TBN (i.e. a TBN of less
than
50), a medium TBN (i.e. a TBN of 50 to 150) or a high TBN (i.e. a TBN of
greater
than 150, such as 150-500).
As stated, 40-90, such as 50-85 or 60-80, mmol of calcium alkyl salicylate per
kg of the composition is provided, the values being determined by titration.
Preferably, the values are in the range of 50-80, more preferably 50-70,
mmol/kg.
POLYALKENYL-SUBSTITUTED CARBOXYLIC ACID ANHYDRIDE (B)
As stated, the anhydride constitutes at least 1 to 7, such as 1.5 to 5 mass %
of
the lubricating oil composition. Preferably it constitutes 2 to 5, for example
3 to 5,
mass %.
9
CA 02810720 2013-03-28
The anhydride may be mono or polycarboxylic, preferably dicarboxylic. The
polyalkenyl group preferably has from 8 to 400, such as 8 to 100, carbon
atoms.
General formulae of exemplary anhydrides may be depicted as
R1
HC¨CO
/0
H2C¨CO
where RI represents a C8 to C100 branched or linear polyalkenyl group:
The polyalkenyl moiety may have a number average molecular weight of from
200 to 3000, preferably from 350 to 950.
Suitable hydrocarbons or polymers employed in the formation of the
anhydrides of the present invention to generate the polyalkenyl moieties
include
homopolymers, interpolymers or lower molecular weight hydrocarbons. One family
of such polymers comprise polymers of ethylene and/or at least one C3 to C28
alpha-
olefin having the formula H2C=CHRI wherein RI is straight or branched chain
alkyl
radical comprising 1 to 26 carbon atoms and wherein the polymer contains
carbon-to-
carbon unsaturation, preferably a high degree of terminal ethenylidene
unsaturation.
Preferably, such polymers comprise interpolymers of ethylene and at least one
alpha-
olefin of the above formula, wherein R1 is alkyl of from 1 to 18 carbon atoms,
and
more preferably is alkyl of from 1 to 8 carbon atoms, and more preferably
still of
from 1 to 2 carbon atoms. Therefore, useful alpha-olefin monomers and
comonomers
include, for example, propylene, butene-1, hexene-1, octene-1, 4-methylpentene-
1,
decene-1, dodecene-1, tridecene- 1, tetradecene- 1, pentadecene -1, hexadecene
-1 ,
heptadecene-1, octadecene-1, nonadecene-1, and mixtures thereof (e.g.,
mixtures of
propylene and butene-1, and the like). Exemplary of such polymers are
propylene
homopolymers, butene-1 homopolymers, ethylene-propylene copolymers, ethylene-
butene-1 copolymers, propylene-butene copolymers and the like, wherein the
polymer
contains at least some terminal and/or internal unsaturation. Preferred
polymers are
unsaturated copolymers of ethylene and propylene and ethylene and butene-1.
The
CA 02810720 2013-03-28
interpolymers may contain a minor amount, e.g. 0.5 to 5 mole % of a C4 to C18
non-
conjugated diolefin comonomer. However, it is preferred that the polymers
comprise
only alpha-olefin homopolymers, interpolymers of alpha-olefin comonomers and
interpolymers of ethylene and alpha-olefin comonomers. The molar ethylene
content
of the polymers employed is preferably in the range of 0 to 80 %, and more
preferably
0 to 60 %. When propylene and/or butene-1 are employed as comonomer(s) with
ethylene, the ethylene content of such copolymers is most preferably between
15 and
50 %, although higher or lower ethylene contents may be present.
These polymers may be prepared by polymerizing alpha-olefin monomer, or
mixtures of alpha-olefin monomers, or mixtures comprising ethylene and at
least one
C3 to C28 alpha-olefin monomer, in the presence of a catalyst system
comprising at
least one metallocene (e.g., a cyclopentadienyl-transition metal compound) and
an
alumoxane compound. Using this process, a polymer in which 95 % or more of the
polymer chains possess terminal ethenylidene-type unsaturation can be
provided. The
percentage of polymer chains exhibiting terminal ethenylidene unsaturation may
be
determined by FTIR spectroscopic analysis, titration, or C13 NMR.
Interpolymers of
this latter type may be characterized by the formula POLY-C(R1)=CH2 wherein
R.' is
CI to C26 alkyl, preferably C1 to C18 alkyl, more preferably Cl to C8 alkyl,
and most
preferably CI to C2 alkyl, (e.g., methyl or ethyl) and wherein POLY represents
the
polymer chain. The chain length of the RI alkyl group will vary depending on
the
comonomer(s) selected for use in the polymerization. A minor amount of the
polymer
chains can contain terminal ethenyl, i.e., vinyl, unsaturation, i.e. POLY-
CH=CH2, and
a portion of the polymers can contain internal monounsaturation, e.g. POLY-
CH=CH(R1), wherein RI is as defined above. These terminally unsaturated
interpolymers may be prepared by known metallocene chemistry and may also be
prepared as described in U.S. Patent Nos. 5,498,809; 5,663,130; 5,705,577;
5,814,715; 6,022,929 and 6,030,930.
Another useful class of polymers is polymers prepared by cationic
polymerization of isobutene, styrene, and the like. Common polymers from this
class
include polyisobutenes obtained by polymerization of a C4 refinery stream
having a
butene content of about 35 to about 75 mass %, and an isobutene content of
about 30
11
CA 02810720 2013-03-28
to about 60 mass %, in the presence of a Lewis acid catalyst, such as aluminum
trichloride or boron trifluoride. A preferred source of monomer for making
poly-n-
butenes is petroleum feedstreams such as Raffinate II. These feedstocks are
disclosed
in the art such as in U.S. Patent No. 4,952,739. Polyisobutylene is a most
preferred
backbone of the present invention because it is readily available by cationic
polymerization from butene streams (e.g., using A1C13 or BF3 catalysts). Such
polyisobutylenes generally contain residual unsaturation in amounts of about
one
ethylenic double bond per polymer chain, positioned along the chain. A
preferred
embodiment utilizes polyisobutylene prepared from a pure isobutylene stream or
a
Raffinate I stream to prepare reactive isobutylene polymers with terminal
vinylidene
olefins. Preferably, these polymers, referred to as highly reactive
polyisobutylene
(HR-PIB), have a terminal vinylidene content of at least 65%, e.g., 70%, more
preferably at least 80%, most preferably, at least 85%. The preparation of
such
polymers is described, for example, in U.S. Patent No. 4,152,499. is known
and HR-PIB is commercially available under the tradenames GlissopalTM (from
BASF) and UltravisTM (from BP-Amoco).
Polyisobutylene polymers that may be employed are generally based on a
hydrocarbon chain of from 400 to 3000. Methods for making polyisobutylene are
known. Polyisobutylene can be functionalized by halogenation (e.g.
chlorination), the
thermal "ene" reaction, or by free radical grafting using a catalyst (e.g.
peroxide), as
described below.
To produce (B) the hydrocarbon or polymer backbone may be functionalized,
with carboxylic anhydride-producing moieties selectively at sites of carbon-to-
carbon
unsaturation on the polymer or hydrocarbon chains, or randomly along chains
using
any of the three processes mentioned above or combinations thereof, in any
sequence.
Processes for reacting polymeric hydrocarbons with unsaturated carboxylic,
anhydrides and the preparation of derivatives from such compounds are
disclosed in
U.S. Patent Nos. 3,087,936; 3,172,892; 3,215,707; 3,231,587; 3,272,746;
3,275,554;
3,381,022; 3,442,808; 3,565,804; 3,912,764; 4,110,349; 4,234,435; 5,777,025;
5,891,953; as well as EP 0 382 450 B 1 ; CA-1,335,895 and GB-A-1,440,219. The
polymer or hydrocarbon may be functionalized, with carboxylic acid anhydride
12
CA 02810720 2013-03-28
moieties by reacting the polymer or hydrocarbon under conditions that result
in the
addition of functional moieties or agents, i.e., acid, anhydride, onto the
polymer or
hydrocarbon chains primarily at sites of carbon-to-carbon unsaturation (also
referred
to as ethylenic or olefinic unsaturation) using the halogen assisted
functionalization
(e.g. chlorination) process or the thermal "ene" reaction.
Selective functionalization can be accomplished by halogenating, e.g.,
chlorinating or brominating the unsaturated a-olefin polymer to about 1 to 8
mass %,
preferably 3 to 7 mass % chlorine, or bromine, based on the weight of polymer
or
hydrocarbon, by passing the chlorine or bromine through the polymer at a
temperature
of 60 to 250 C, preferably 110 to 160 C, e.g., 120 to 140 C, for about 0.5 to
10,
preferably 1 to 7 hours. The halogenated polymer or hydrocarbon (hereinafter
backbone) is then reacted with sufficient monounsaturated reactant capable of
adding
the required number of functional moieties to the backbone, e.g.,
monounsaturated
carboxylic reactant, at 100 to 250 C, usually about 180 C to 235 C, for about
0.5 to
10, e.g., 3 to 8 hours, such that the product obtained will contain the
desired number
of moles of the monounsaturated carboxylic reactant per mole of the
halogenated
backbones. Alternatively, the backbone and the monounsaturated carboxylic
reactant
are mixed and heated while adding chlorine to the hot material.
While chlorination normally helps increase the reactivity of starting olefin
polymers with monounsaturated functionalizing reactant, it is not necessary
with
some of the polymers or hydrocarbons contemplated for use in the present
invention,
particularly those preferred polymers or hydrocarbons which possess a high
terminal
bond content and reactivity.
Preferably, therefore, the backbone and the
monounsaturated functionality reactant, (carboxylic reactant), are contacted
at
elevated temperature to cause an initial thermal "ene" reaction to take place.
Ene
reactions are known.
The hydrocarbon or polymer backbone can be functionalized by random
attachment of functional moieties along the polymer chains by a variety of
methods.
For example, the polymer, in solution or in solid form, may be grafted with
the
monounsaturated carboxylic reactant, as described above, in the presence of a
free-
13
CA 02810720 2013-03-28
=
radical initiator. When performed in solution, the grafting takes place at an
elevated
temperature in the range of about 100 to 260 C, preferably 120 to 240 C.
Preferably,
free-radical initiated grafting would be accomplished in a mineral lubricating
oil
solution containing, e.g., 1 to 50 mass %, preferably 5 to 30 mass % polymer
based on
the initial total oil solution.
The free-radical initiators that may be used are peroxides, hydroperoxides,
and
azo compounds, preferably those that have a boiling point greater than about
100 C
and decompose thermally within the grafting temperature range to provide free-
radicals. Representative of these free-radical initiators are
azobutyronitrile, 2,5-
dimethylhex-3-ene-2, 5-bis-tertiary-butyl peroxide and dicumene peroxide. The
initiator, when used, typically is used in an amount of between 0.005% and 1%
by
weight based on the weight of the reaction mixture solution. Typically, the
aforesaid
monounsaturated carboxylic reactant material and free-radical initiator are
used in a
weight ratio range of from about 1.0:1 to 30:1, preferably 3:1 to 6:1. The
grafting is
preferably carried out in an inert atmosphere, such as under nitrogen
blanketing. The
resulting grafted polymer is characterized by having carboxylic acid (or
derivative)
moieties randomly attached along the polymer chains: it being understood, of
course,
that some of the polymer chains remain ungrafted. The free radical grafting
described
above can be used for the other polymers and hydrocarbons of the present
invention.
The preferred monounsaturated reactants that are used to functionalize the
backbone comprise mono- and dicarboxylic acid material, i.e., acid, or acid
derivative
material, including (i) monounsaturated C4 to C10 dicarboxylic acid wherein
(a) the
carboxyl groups are vicinyl, (i.e., located on adjacent carbon atoms) and (b)
at least
one, preferably both, of said adjacent carbon atoms are part of said mono
unsaturation; (ii) derivatives of (i) such as anhydrides or C1 to C5 alcohol
derived
mono- or diesters of (i); (iii) monounsaturated C3 to Ci0monocarboxylic acid
wherein
the carbon-carbon double bond is conjugated with the carboxy group, i.e., of
the
structure -C=C-00-; and (iv) derivatives of (iii) such as C1 to C5 alcohol
derived
mono- or diesters of (iii). Mixtures of monounsaturated carboxylic materials
(i) - (iv)
also may be used. Upon reaction with the backbone, the monounsaturation of the
monounsaturated carboxylic reactant becomes saturated. Thus, for example,
maleic
anhydride becomes backbone-substituted succinic anhydride, and acrylic acid
14
CA 02810720 2013-03-28
becomes backbone-substituted propionic acid. Exemplary of such monounsaturated
carboxylic reactants are fumaric acid, itaconic acid, maleic acid, maleic
anhydride,
chloromaleic acid, chloromaleic anhydride, acrylic acid, methacrylic acid,
crotonic
acid, cinnamic acid, and lower alkyl (e.g., C1 to C4 alkyl) acid esters of the
foregoing,
e.g., methyl maleate, ethyl fumarate, and methyl fumarate.
To provide the required functionality, the monounsaturated carboxylic
reactant,
preferably maleic anhydride, typically will be used in an amount ranging from
about
equimolar amount to about 100 mass % excess, preferably 5 to 50 mass % excess,
based on the moles of polymer or hydrocarbon. Unreacted excess monounsaturated
carboxylic reactant can be removed from the final dispersant product by, for
example,
stripping, usually under vacuum, if required.
The treat rate of additives (A) and (B) contained in the lubricating oil
composition may for example be in the range of 1 to 2.5, preferably 2 to 20,
more
preferably 5 to 18, mass %.
CO-ADDITIVES
The lubricating oil composition of the invention may comprise further
additives, different from and additional to (A) and (B). Such additional
additives may,
for example include ashless dispersants, other metal detergents, anti-wear
agents such
as zinc dihydrocarbyl dithiophosphates, anti-oxidants and demulsifiers. In
some cases,
an ashless dispersant need not be provided.
It may be desirable, although not essential, to prepare one or more additive
packages or concentrates comprising the additives, whereby additives (A) and
(B) can
be added simultaneously to the base oil to form the lubricating oil
composition.
Dissolution of the additive package(s) into the lubricating oil may be
facilitated by
solvents and by mixing accompanied with mild heating, but this is not
essential. The
additive package(s) will typically be formulated to contain the additive(s) in
proper
amounts to provide the desired concentration, and/or to carry out the intended
function in the final formulation when the additive package(s) is/are combined
with a
CA 02810720 2013-03-28
predetermined amount of base lubricant. Thus, additives (A) and (B), in
accordance
with the present invention, may be admixed with small amounts of base oil or
other
compatible solvents together with other desirable additives to form additive
packages
containing active ingredients in an amount, based on the additive package, of,
for
example, from 2.5 to 90, preferably from 5 to 75, most preferably from 8 to
60,
mass % of additives in the appropriate proportions, the remainder being base
oil.
The final formulations as a trunk piston engine oil may typically contain 30,
preferably 10 to 28, more preferably 12 to 24, mass % of the additive
package(s), the
remainder being base oil. The trunk piston engine oil has a compositional TBN
(using ASTM D2896) of 20 to 60, such as, 30 to 55. For example, it may be 40
to 55
or 35 to 50. When the TBN is high, for example 45-55, the concentration of (A)
may
be higher. When the TBN is lower, for example 30 to below 45, the
concentration of
(A) may be lower.
The present invention is illustrated by but in no way limited to the following
examples.
COMPONENTS
The following components were used:
Component (Al): a calcium alkyl salicylate detergent comprising a mixture
of a
first calcium alkyl salicylate detergent (basicity index 3) and a
second calcium alkyl salicylate detergent (basicity index 7.8) in
a ratio of 0.85:1
Component (A2): a calcium alkyl salicylate detergent comprising a mixture
of the
above first and second detergents, but in a ratio of 0.62:1
Component (A3): a calcium alkyl salicylate detergent comprising a mixture
of the
above first and second detergents, but in a ratio of 0.28:1
16
CA 02810720 2013-03-28
Component (B): a polyisobutene succinic anhydride ("PIBSA") derived from a
polyisobutene having a number average molecular weight of
950
Base oil I: solvent-extracted API Group I base oil
HFO: a heavy fuel oil (ISO-F-RMK 380)
LUBRICANTS
Selections of the above components were blended to give a range of trunk
piston marine engine lubricants. Some of the lubricants are examples of the
invention; others are reference examples for comparison purposes. The
compositions
of the lubricants tested when each contained HFO are shown in the tables below
under
the "Results" heading.
TESTING
Light Scattering
Test lubricants were evaluated for asphaltene dispersancy using light
scattering according to the Focused Beam Reflectance Method ("FBRM"), which
predicts asphaltene agglomeration and hence 'black sludge' formation.
The FBRM test method was disclosed at the 7th International Symposium on
Marine Engineering, Tokyo, 24th - 28th October 2005, and was published in 'The
Benefits of Salicylate Detergents in TPEO Applications with a Variety of Base
Stocks', in the Conference Proceedings. Further details were disclosed at the
CIMAC
Congress, Vienna, 21st -24th May 2007 and published in "Meeting the Challenge
of
New Base Fluids for the Lubrication of Medium Speed Marine Engines ¨ An
Additive Approach" in the Congress Proceedings. In the latter paper it is
disclosed
that by using the FBRM method it is possible to obtain quantitative results
for
asphaltene dispersancy that predict performance for lubricant systems based on
base
stocks containing greater than or less than 90% saturates, and greater than or
less than
17
CA 02810720 2013-03-28
0.03% sulphur. The predictions of relative performance obtained from FBRM were
confirmed by engine tests in marine diesel engines.
The FBRM probe contains fibre optic cables through which laser light travels
to reach the probe tip. At the tip, an optic focuses the laser light to a
small spot. The
optic is rotated so that the focussed beam scans a circular path between the
window of
the probe and the sample. As particles flow past the window, they intersect
the
scanning path, giving backscattered light from the individual particles.
The scanning laser beam travels much faster than the particles; this means
that
the particles are effectively stationary. As the focussed beam reaches one
edge of the
particle the amount of backscattered light increases; the amount will decrease
when
the focussed beam reaches the other edge of the particle.
The instrument measures the time of the increased backscatter. The time
period of backscatter from one particle is multiplied by the scan speed and
the result
is a distance or chord length. A chord length is a straight line between any
two points
on the edge of a particle. This is represented as a chord length distribution,
a graph of
numbers of chord lengths (particles) measured as a function of the chord
length
dimensions in microns. As the measurements are performed in real time, the
statistics
of a distribution can be calculated and tracked. FBRM typically measures tens
of
thousands of chords per second, resulting in a robust number-by-chord length
distribution. The method gives an absolute measure of the particle size
distribution of
the asphaltene particles.
The Focused beam Reflectance Probe (FBRM), model Lasentec D600L, was
supplied by Mettler Toledo, Leicester, UK. The instrument was used in a
configuration to give a particle size resolution of 1 um to lmm. Data from
FBRM can
be presented in several ways. Studies have suggested that the average counts
per
second can be used as a quantitative determination of asphaltene dispersancy.
This
value is a function of both the average size and level of agglomerate. In this
application, the average count rate (over the entire size range) was monitored
using a
measurement time of 1 second per sample.
18
CA 02810720 2013-03-28
The test lubricant formulations were heated to 60 C and stirred at 400rpm;
when the temperature reached 60 C the FBRM probe was inserted into the sample
and measurements made for 15 minutes. An aliquot of heavy fuel oil (10% w/w)
was
introduced into the lubricant formulation under stiffing using a four-blade
stirrer (at
400 rpm). A value for the average counts per second was taken when the count
rate
had reached an equilibrium value (typically overnight).
RESULTS
Light Scattering
The results of the FBRM tests are summarized in TABLE 1 below, where
lower particle count indicates better performance.
Reference examples designated "Ref'. Examples marked with an asterisk are for
reference or comparison purposes only.
19
CA 02810720 2013-03-28
TABLE 1
Ex PIBSA Detergent (soap level)
(mass /0 Al) Al A2 A3
(80mmol) (70mmol) (60mmol)
-
Ref 0 4,528.93* 6,0603*
6,232.42*
1 0.72 2,239.37* 1,955.4 3,693.09
2 2.16 47.97* 52.53 104.64
-
3 3.6 40.28* 47.56 31.83
4 7.2 32.67* 36.48 29.91
The results show that, when PIBSA is absent (as in the reference examples),
performance is better when the soap level is higher. When PIBSA is present,
(as in
Examples 1-4), the performance may, at lower soap levels, be as good as or
better
than the performance at higher soap levels.
